Aryl benzoyl urea derivative and pesticidal composition comprising the same

ABSTRACT

The present invention relates to a novel aryl benzoyl urea derivative represented by formula (I), in which X 1  and X 2  independently of one another represent hydrogen, fluoro, chloro or bromo, R 1  represents chloro, bromo or trifluoromethyl, one of R 2  and R 4  is hydrogen and the other represents fluoro, chloro, bromo, cyano or trifluoromethyl, and R 3  represents fluoro, chloro, bromo or cyano, which has a potent growth-retarding activity against pests. ##STR1##

This application claims the benefit under 35 U.S.C. §371 of prior PCTInternational Application No. PCT/KR96/00196 which has an Internationalfiling date of Nov. 7, 1996 which designated the United States ofAmerica, the entire contents of which are hereby incorporated byreferences.

TECHNICAL FIELD

The present invention relates to a novel aryl benzoylurea derivativehaving a potent growth-retarding activity against pests. Morespecifically, the present invention relates to a novel aryl benzoylureaderivative represented by the following formula (I): ##STR2## in whichX¹ and X² independently of one another represent hydrogen, fluoro,chloro or bromo,

R¹ represents chloro, bromo or trifluoromethyl,

one of R² and R⁴ is hydrogen and the other represents fluoro, chloro,bromo, cyano or trifluoromethyl, and

R³ represents fluoro, chloro, bromo or cyano.

The present invention also relates to a process for preparing thecompound of formula (I), as defined above, and a pesticidal compositioncomprising the compound of formula (I) as an active ingredient.

BACKGROUND ART

Before the present invention, several kinds of benzoyl urea compoundshave been developed as an inhibitor for chitin formation. As typicalexamples commercially available,N-(2,6-difluorobenzoyl)-N'-(4-chlorophenyl)urea described in U.S. Pat.No. 3,933,908 and N-(2,6-difluorobenzoyl)-N'-(3,4-dichlorophenyl)ureadescribed in U.S. Pat. No. 4,166,124 can be mentioned, which were theinitiation of the developments of benzoyl urea-based pesticides.

European Patent Publication Nos. 093,976 and 093,977 disclose arylbenzoyl urea derivatives having a similar structure to the desiredcompound of the present invention. However, they are different from thecompound (I) of the present invention in that all the substituents ofR², R³ and R⁴ are some groups other than hydrogen, or R³ position issubstituted with an ether group. Furthermore, their pesticidal spectrumis restricted to Plutella. And compounds with good pesticidal activityamong them are mainly benzoyl ureido diphenyl ether derivatives, whichcan be prepared only through complicated and uneconomic processes.

In addition, European Patent Publication No. 232,080 discloses benzoylurea derivative of which aryl moiety is 2,5-difluoro-4-chlorophenyl.However, since LC₅₀ thereof against Spodoptera is 0.3 to 0.4 ppm, it hasa much lower activity than the compound according to the presentinvention having 0.1 ppm or less of LC₅₀ against the same pest.

While, International Patent Application No. PCT/KR95/00072, which wasfiled by the present applicant, discloses phenyl benzoyl(nicotinoyl)urea derivatives wherein R³ position is fixedly substituted withhydrogen, which is different from the compound of the present inventionwherein R³ position is substituted with halogen or cyano. Further, withrespect to the pesticidal activity against both Plutella xylostella andSpodoptera litura, the compound of the present invention is superior tothat described in the International Patent Appln. No. PCT/KR95/00072.

DISCLOSURE OF INVENTION

The present inventors have extensively studied to develop a novel arylbenzoyl urea derivative which can be prepared by a convenient processand as well exhibits a superior pesticidal activity even at a lowconcentration. As a result of such studies, we have identified that anaryl benzoyl urea derivative of the formula (I) above has never beendisclosed in any prior publications and can satisfy such requirements,and thus completed the present invention.

Accordingly, it is an object of the present invention to provide a novelaryl benzoyl urea derivative represented by the following formula (I):##STR3## in which X¹ and X² independently of one another representhydrogen, fluoro, chloro or bromo,

R¹ represents chloro, bromo or trifluoromethyl,

one of R² and R⁴ is hydrogen and the other represents fluoro, chloro,bromo, cyano or trifluoromethyl, and

R³ represents fluoro, chloro, bromo or cyano.

It is another object of the present invention to provide a process forpreparing the novel aryl benzoyl urea derivative of formula (I):##STR4## in which X¹ and X² independently of one another representhydrogen, fluoro, chloro or bromo,

R¹ represents chloro, bromo or trifluoromethyl,

one of R² and R⁴ is hydrogen and the other represents fluoro, chloro,bromo, cyano or trifluoromethyl, and

R³ represents fluoro, chloro, bromo or cyano, characterized in that abenzoyl isocyanate having the following formula (II): ##STR5## in whichX¹ and X² are defined as previously described, is reacted with ananiline derivative having the following formula (III): ##STR6## in whichR¹, R², R³ and R⁴ are defined as previously described in the presence ofa diluent.

It is a further object of the present invention to provide a pesticidalcomposition comprising the aryl benzoyl urea derivative of formula (I)as an active ingredient, in combination with an agriculturallyacceptable carrier.

BEST MODE FOR CARRYING OUT THE INVENTION

In one aspect, the present invention relates to a novel aryl benzoylurea derivative having the following formula (I), which has a potentpesticidal activity: ##STR7## in which X¹ and X² independently of oneanother represent hydrogen, fluoro, chloro or bromo,

R¹ represents chloro, bromo or trifluoromethyl,

one of R² and R⁴ is hydrogen and the other represents fluoro, chloro,bromo, cyano or trifluoromethyl, and

R³ represents fluoro, chloro, bromo or cyano.

Among the compound of formula (I) according to the present invention,the preferred one includes those wherein X¹ and X² independently of oneanother represent hydrogen, fluoro or chloro, R¹ represents chloro,bromo or trifluoromethyl, one of R² and R⁴ is hydrogen and the otherrepresents chloro, bromo or trifluoromethyl, and R³ represents fluoro,chloro, bromo or cyano.

Typical examples of the compound of formula (I) according to the presentinvention are as follows:

1-(2-bromo-4-chloro-5-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea;

1-(2-bromo-4-chloro-5-trifluoromethylphenyl)-3-(2-fluorobenzoyl)urea;

1-(2-bromo-4-chloro-5-trifluoromethylphenyl)-3-(2-chlorobenzoyl)urea;

1-(2-bromo-4-chloro-5-trifluoromethylphenyl)-3-(2-bromobenzoyl)urea;

1-(4,5-dibromo-2-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea;

1-(4,5-dibromo-2-trifluoromethylphenyl)-3-(2,6-dichlorobenzoyl)urea;

1-(2,4-dibromo-5-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea;

1-(2,4-dibromo-5-trifluoromethylphenyl)-3-(2-chlorobenzoy)urea;

1-(2,4-dibromo-5-trifluoromethylphenyl)-3-(2-fluorobenzoyl)urea;

1-(2-bromo-5-chloro-4-cyanophenyl)-3-(2,6-difluorobenzoyl)urea;

1-(2-bromo-4-fluoro-5-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea;

1-(2-bromo-4-fluoro-5-trifluoromethylphenyl)-3-(2-fluorobenzoyl)urea;

1-(2-bromo-4-fluoro-5-trifluoromethylphenyl)-3-(2-chlorobenzoyl)urea;

1-(2-chloro-4-fluoro-5-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea;

1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea;

1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2-fluorobenzoyl)urea;

1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2-chlorobenzoyl)urea;

1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2,6-dichlorobenzoyl)urea;

1-(2,3-dichloro-4-cyanophenyl)-3-(2,6-difluorobenzoyl)urea;

1-(2,3-dichloro-4-cyanophenyl)-3-(2-fluorobenzoyl)urea;

1-(2,3-dichloro-4-cyanophenyl)-3-(2-chlorobenzoyl)urea;

1-(2,5-dichloro-4-cyanophenyl)-3-(2,6-difluorobenzoyl)urea;

1-(2,5-dichloro-4-cyanophenyl)-3-(2-chlorobenzoyl)urea;

In another aspect, the present invention relates to a process forpreparing the compound of formula (I) as defined above.

According to the process of the present invention, the desired arylbenzoyl urea derivative of formula (I) can be prepared by reacting abenzoyl isocyanate of formula (II) with an aniline derivative of formula(III) in a suitable diluent, as shown in the following reaction scheme:##STR8## In the above reaction scheme, X¹, X², R¹, R², R³ and R⁴ aredefined as previously described.

The reaction of the compound of formula (II) with the compound offormula (III) according to the present invention can be carried out inthe presence of a diluent. For this purpose, any inert organic solventcan be used unless it adversely affect the reaction. Particularly, thediluent which can be preferably used in this reaction includesoptionally chlorinated aliphatic or aromatic hydrocarbons such asbenzene, toluene, xylene, methylene chloride, chloroform, carbontetrachloride, 1,2-dichloroethane, tetrahydrofuran or chlorobenzene;ethers such as diethyl ether, dibutyl ether or dioxane; ketones such asacetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutylketone; and nitriles such as acetonitrile or propionitrile, and thelike. The reaction can be generally carried out at the temperature of 0to 1200° C., preferably 10 to 50° C., under room pressure.

In this reaction, the reactants are preferably used in an equimolaramount. Although any one of the reactants can be used in an excessiveamount, it is not advantageous in view of economics in either industrialscale or laboratory.

The aryl benzoyl urea compound of formula (I) is prepared by stirringthe reactants for 2 hours or more in the inert diluent as mentionedabove at the temperature as defined above and then filtering theresulting product in vacuo. All the products thus obtained are presentin the form of a crystral, have definite melting points, and areidentified by NMR spectrum.

The benzoyl isocyanate compound of formula (II) used in the abovereaction as a starting material can be prepared by reacting thesubstituted benzamide represented by the following formula (IV) with anoxalyl chloride in the presence of an organic solvent. As the organicsolvent, benzene, toluene, xylene, chlorobenzene or 1,2-dichloroethanecan be used, and the reaction should be proceeded until no more gasesare generated. ##STR9## in which, X¹ and X² are defined as previouslydescribed.

Typical examples of the novel aryl benzoyl urea derivative of formula(I) prepared according to the present invention are listed in thefollowing table 1.

                  TABLE 1                                                         ______________________________________                                        COM. No.                                                                             X.sup.1  & X.sup.2                                                                     R.sup.1 R.sup.2                                                                             R.sup.3                                                                            R.sup.4                                                                             M.P. (° C.)                   ______________________________________                                         1     2,6-F.sub.2                                                                            Br      H     Cl   CF.sub.3                                                                            196                                     2 2-F Br H Cl CF.sub.3 170                                                    3 2-Cl Br H Cl CF.sub.3 185                                                   4 2-Br Br H Cl CF.sub.3 193                                                   5 2,6-F.sub.2 CF.sub.3 H Br Br 203                                            6 2,6-Cl.sub.2 CF.sub.3 H Br Br 204                                           7 2,6-F.sub.2 Br H Br CF.sub.3 197                                            8 2-Cl Br H Br CF.sub.3 191                                                   9 2-F Br H Br CF.sub.3 181                                                   10 2,6-F.sub.2 Br H CN Cl 247                                                 11 2,6-F.sub.2 Br H F CF.sub.3 181                                            12 2-F Br H F CF.sub.3 171                                                    13 2-Cl Br H F CF.sub.3 192                                                   14 2,6-F.sub.2 Cl H F CF.sub.3 192                                            15 2,6-F.sub.2 Cl CF.sub.3 F H 214                                            16 2-F Cl CF.sub.3 F H 173                                                    17 2-Cl Cl CF.sub.3 F H 208                                                   18 2,6-Cl.sub.2 Cl CF.sub.3 F H 227-230                                       19 2,6-F.sub.2 Cl Cl CN H 285-287                                             20 2-F Cl Cl CN H 298-300                                                     21 2-Cl Cl Cl CN H 278-282                                                    22 2,6-F.sub.2 Cl H CN Cl 238-240                                             23 2-Cl Cl H CN Cl 244-247                                                  ______________________________________                                    

The compound according to the present invention as mentioned above canbe effectively used as a pesticide in agricultural field. Particularly,the compound of the present invention combats the pest through amechanism to inhibit a chitin synthesis which results in the inhibitionof peeling off the insect skin, and therefore, is less toxic to mammals.The compound of the present invention can also be utilized forprotection of farm lands, forests, stored goods, and the like. It isgenerally active against not only sensitive or resistant species butalso inserts under all the growth stages.

The present invention will be more specifically explained by thefollowing examples. However, it should be understood that the examplesare intended to illustrate and not to limit the scope of the presentinvention in any manner.

EXAMPLE 1 Preparation of1-(2-bromo-4-chloro-5-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea

0.49 g (3.1 mmol) of 2,6-difluorobenzamide and 0.43 g (3.4 mmol, 1.1 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-difluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.85 g (3.1 mmol) of2-bromo-4-chloro-5-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 0.82 g (Yield 76%)of the title compound as a solid.

M.P.: 196° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.94(s,1H), 10.94 (s,1H),8.68(s,1H), 8.16(s,1H), 7.70-7.60(m,1H), 7.29-7.23(t,2H).

EXAMPLE 2 Preparation of1-(2-bromo-4-chloro-5-trifluoromethylphenyl)-3-(2-fluorobenzoyl)urea

0.43 g (3.1 mmol) of 2-fluorobenzamide and 0.43 g (3.4 mmol, 1.1 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-fluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.85 g (3.1 mmol) of2-bromo-4-chloro-5-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 0.82 g (Yield 60%)of the title compound as a solid.

M.P.: 170° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.50(s, 1H), 11.25 (s,1H),8.73(s,1H), 8.16(s,1H), 7.74-7.62(m,2H), 7.39-7.32(m, 2H).

EXAMPLE 3 Preparation of1-(2-bromo-4-chloro-5-trifluoromethylphenyl)-3-(2-chlorobenzoyl)urea

0.39 g (2.5 mmol) of 2-chlorobenzamide and 0.38 g (3.0 mmol, 1.2 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-chlorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.69 g (2.5 mmol) of2-bromo-4-chloro-5-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 0.61 g (Yield 53%)of the title compound as a solid.

M.P.: 185° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.68(s,1H), 11.19 (s,1H),8.74(s,1H), 8.17(s,₁ H), 7.65-7.44(m,4H).

EXAMPLE 4 Preparation of1-(2-bromo-4-chloro-5-trifluoromethylphenyl)-3-(2-bromobenzoyl)urea

0.47 g (2.3 mmol) of 2-bromobenzamide and 0.34 g (2.7 mmol, 1.2 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-bromobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.64 g (2.3 mmol) of2-bromo-4-chloro-5-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 0.25 g (Yield 22%)of the title compound as a solid.

M.P.: 193° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.66(s,1H), 11.18 (s,1H),8.75(s,1H), 8.19(s,1H), 7.75-7.44(m,4H).

EXAMPLE 5 Preparation of1-(4,5-dibromo-2-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea

0.34 g (2.2 mmol) of 2,6-difluorobenzamide and 0.33 g (2.6 mmol, 1.2 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-difluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.69 g (2.2 mmol) of4,5-dibromo-2-trifluoromethyl aniline were successively added thereto,reacted for 2 hours and filtered to obtain 0.61 g (Yield 56%) of thetitle compound as a solid.

M.P.: 203° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.64(s,1H), 9.91 (s,1H), 8.39(s,1H),8.03(s,1H), 7.69-7.59(m,1H), 7.29-7.23(t,2H).

EXAMPLE 6 Preparation of1-(4,5-dibromo-2-trifluoromethylphenyl)-3-(2,6-dichlorobenzoyl)urea

0.51 g (2.7 mmol) of 2,6-dichlorobenzamide and 0.41 g (3.2 mmol, 1.2 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-dichlorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.86 g (2.7 mmol) of4,5-dibromo-2-trifluoromethyl aniline were successively added thereto,reacted for 2 hours and filtered to obtain 0.28 g (Yield 43%) of thetitle compound as a solid.

M.P.: 204° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.63(s,1H), 9.98 (s,1H), 8.39(s,1H),8.03(s,1H), 7.61-7.51(m,3H).

EXAMPLE 7 Preparation of1-(2,4-dibromo-5-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea

0.47 g (3.0 mmol) of 2,6-difluorobenzamide and 0.40 g (3.2 mmol, 1.05eq) of oxalyl chloride were added to 10 ml of 1,2-dichloroethane andthen the mixture was stirred for 8 hours at 100° C. The reactionsolution was cooled down to room temperature. The reaction solvent andexcessive oxalyl chloride were removed by distillation under reducedpressure to obtain 2,6-difluorobenzoyl isocyanate in an oily state. 10ml of fresh 1,2-dichloroethane and 0.95 g (3.0 mmol) of2,4-dibromo-5-trifluoromethyl aniline were successively added thereto,reacted for 2 hours and filtered to obtain 1.15 g (Yield 76%) of thetitle compound as a solid.

M.P.: 197° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.95(s,1H), 10.95 (s,1H),8.71(s,1H), 8.33(s,1H), 7.72-7.62(m,1H), 7.32-7.26(t,2H).

EXAMPLE 8 Preparation of1-(2,4-dibromo-5-trifluoromethylphenyl)-3-(2-chlorobenzoyl)urea

0.47 g (3.0 mmol) of 2-chlorobenzamide and 0.40 g (3.2 mmol, 1.05 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-chlorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.95 g (3.0 mmol) of2,4-dibromo-5-trifluoromethyl aniline were successively added thereto,reacted for 2 hours and filtered to obtain 1.2 g (Yield 80%) of thetitle compound as a solid.

M.P.: 191° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.68(s,1H), 11.20 (s,1H),8.77(s,1H), 8.33(s,1H), 7.67-7.45(m,4H).

EXAMPLE 9 Preparation of1-(2,4-dibromo-5-trifluoromethylphenyl)-3-(2-fluorobenzoyl)urea

0.47 g (3.0 mmol) of 2-fluorobenzamide and 0.40 g (3.2 mmol, 1.05 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-fluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.95 g (3.0 mmol) of2,4-dibromo-5-trifluoromethyl aniline were successively added thereto,reacted for 2 hours and filtered to obtain 1.11 g (Yield 77%) of thetitle compound as a solid.

M.P.: 181° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ11.53(s,1H), 11.26 (s,1H), 8.77(s,1H),8.33(s,1H), 7.76-7.63(m,2H), 7.42-7.34(m,2H).

EXAMPLE 10 Preparation of1-(2-bromo-5-chloro-4-cyanophenyl)-3-(2,6-difluorobenzoyl)urea

0.27 g (1.7 mmol) of 2,6-difluorobenzamide and 0.22 g (1.9 mmol, 1.1 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-difluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.40 g (1.7 mmol) of 2-bromo-5-chloro-4-cyanoaniline were successively added thereto, reacted for 2 hours andfiltered to obtain 0.54 g (Yield 76%) of the title compound as a solid.

M.P.: 247° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 12.07(s,1H), 11.13 (s,1H),8.57(s,1H), 8.47(s,1H), 7.73-7.63(m,1H) , 7.32-7.26(t,2H).

EXAMPLE 11 Preparation of1-(2-bromo-4-fluoro-5-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea

0.43 g (2.7 mmol) of 2,6-difluorobenzamide and 0.36 g (2.9 mmol, 1.1 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-difluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.7 g (2.7 mmol) of2-bromo-4-fluoro-5-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 1.05 g (Yield 88%)of the title compound as a solid.

M.P.: 181° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.88(s,1H), 10.81 (s,1H),8.56(s,1H), 8.13-8.09(d,1H), 7.71-7.61(m,1H), 7.31-7.26 (t,2H).

EXAMPLE 12 Preparation of1-(2-bromo-4-fluoro-5-trifluoromethylphenyl)-3-(2-fluorobenzoyl)urea

0.38 g (2.7 mmol) of 2-fluorobenzamide and 0.36 g (2.9 mmol, 1.1 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-fluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.7 g (2.7 mmol) of2-bromo-4-fluoro-5-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 1.06 g (Yield 93%)of the title compound as a solid.

M.P.: 171° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.48(s,1H), 11.15 (s,1H),8.63-8.61(d,1H), 8.12-8.09(d,1H), 7.76-7.63(m,2H), 7.41-7.33(q,2H).

EXAMPLE 13 Preparation of1-(2-bromo-4-fluoro-5-trifluoromethylphenyl)-3-(2-chlorobenzoyl)urea

0.42 g (2.7 mmol) of 2-chlorobenzamide and 0.36 g (2.9 mmol, 1.1 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-chlorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.7 g (2.7 mmol) of2-bromo-4-fluoro-5-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 1.0 g (Yield 84%) ofthe title compound as a solid.

M.P.: 192° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.76(s,1H), 10.94 (s,1H),8.62-8.57(m,2H), 8.17-8.10(m,2H), 7.61-7.57(q,1H).

EXAMPLE 14 Preparation of1-(2-chloro-4-fluoro-5-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea

0.16 g (1.0 mmol) of 2,6-difluorobenzamide and 0.14 g (1.1 mmol, 1.1 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-difluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.2 g (1.0 mmol) of2-chloro-4-fluoro-5-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 0.29 g (Yield 73%)of the title compound as a solid.

M.P.: 192° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.90(s,1H), 10.87 (s,1H),8.60(s,1H), 8.03-7.99(d,1H), 7.71-7.61(m,1H), 7.31-7.26(t,2H).

EXAMPLE 15 Preparation of1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea

0.25 g (1.6 mmol) of 2,6-difluorobenzamide and 0.22 g (1.8 mmol, 1.1 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-difluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.3 g (1.6 mmol) of2-chloro-4-fluoro-3-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 0.45 g (Yield 73%)of the title compound as a solid.

M.P.: 214° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.85(s,1H), 10.81 (s,1H),8.47(s,1H), 7.71-7.54(m,2H), 7.31-7.25(t,2H).

EXAMPLE 16 Preparation of1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2-fluorobenzoyl)urea

0.22 g (1.6 mmol) of 2-fluorobenzamide and 0.22 g (1.8 mmol, 1.1 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-fluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.3 g (1.6 mmol) of2-chloro-4-fluoro-3-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 0.42 g (Yield 67%)of the title compound as a solid.

M.P.: 173° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.45(s,1H), 11.16 (s,1H),8.53(s,1H), 7.77-7.55(m,3H), 7.41-7.33(m,2H).

EXAMPLE 17 Preparation of1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2-chlorobenzoyl)urea

0.25 g (1.6 mmol) of 2-chlorobenzamide and 0.22 g (1.8 mol, 1.1 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-chlorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.3 g (1.6 mmol) of2-chloro-4-fluoro-3-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 0.53 g (Yield 84%)of the title compound as a solid.

M.P.: 208° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.60(s,1H), 11.08 (s,1H),8.53(s,1H), 7.67-7.45(m,5H).

EXAMPLE 18 Preparation of1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2,6-dichlorobenzoyl)urea

0.30 g (1.6 mmol) of 2,6-dichlorobenzamide and 0.22 g (1.8 mmol, 1.1 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-dichlorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.3 g (1.6 mmol) of2-chloro-4-fluoro-3-trifluoromethyl aniline were successively addedthereto, reacted for 2 hours and filtered to obtain 0.58 g (Yield 84%)of the title compound as a solid.

M.P.: 227-230° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.93(s,1H), 10.94 (s,1H),8.51(s,1H), 7.62-7.52(m,5H).

EXAMPLE 19 Preparation of1-(2,3-dichloro-4-cyanophenyl)-3-(2,6-difluorobenzoyl)urea

0.24 g (1.5 mmol) of 2,6-difluorobenzamide and 0.19 g (1.6 mmol, 1.1 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-difluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.3 g (1.5 mmol) of 2,3-dichloro-4-cyano anilinewere successively added thereto, reacted for 2 hours and filtered toobtain 0.41 g (Yield 73%) of the title compound as a solid.

M.P.: 285-287° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 12.04(s,1H), 11.22 (s,1H),8.48-8.45(d,1H), 8.02-8.00(d,1H), 7.70-7.65(m,1H), 7.32-7.26(t,2H).

EXAMPLE 20 Preparation of1-(2,3-dichloro-4-cyanophenyl)-3-(2-fluorobenzoyl)urea

0.24 g (1.5 mmol) of 2-fluorobenzamide and 0.19 g (1.6 mmol, 1.1 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-fluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.28 g (1.5 mmol) of 2,3-dichloro-4-cyano anilinewere successively added thereto, reacted for 2 hours and filtered toobtain 0.41 g (Yield 73%) of the title compound as a solid.

M.P.: 298-300° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.56(s,1H), 11.28 (s,1H),8.53-8.50(d,1H), 8.03-8.00(d,1H), 7.77-7.62(M,2H), 7.42-7.33(m,2H).

EXAMPLE 21 Preparation of1-(2,3-dichloro-4-cyanophenyl)-3-(2-chlorobenzoyl)urea

0.23 g (1.5 mmol) of 2-chlorobenzamide and 0.19 g (1.6 mmol, 1.1 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-chlorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.28 g (1.5 mmol) of 2,3-dichloro-4-cyano anilinewere successively added thereto, reacted for 2 hours and filtered toobtain 0.25 g (Yield 45%) of the title compound as a solid.

M.P.: 278-282° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.79(s,1H), 11.48 (s,1H),8.52-8.49(d,1H), 8.03-8.00(d,1H), 7.68-7.45(m,4H).

EXAMPLE 22

Preparation of1-(2,5-dichloro-4-cyanophenyl)-3-(2,6-difluorobenzoyl)urea

0.24 g (1.5 mmol) of 2,6-difluorobenzamide and 0.19 g (1.6 mmol, 1.1 eq)of oxalyl chloride were added to 10 ml of 1,2-dichloroethane and thenthe mixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2,6-difluorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.28 g (1.5 mmol) of 2,5-dichloro-4-cyano anilinewere successively added thereto, reacted for 2 hours and filtered toobtain 0.38 g (Yield 69%) of the title compound as a solid.

M.P.: 238-240° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 12.08(s,1H), 11.18 (s,1H),8.60(s,1H), 8.37(s,1H), 7.72-7.62(m,1H), 7.32-7.26 (t,2H).

EXAMPLE 23 Preparation of1-(2,5-dichloro-4-cyanophenyl)-3-(2-chlorobenzoyl)urea

0.23 g (1.5 mmol) of 2-chlorobenzamide and 0.19 g (1.6 mmol, 1.1 eq) ofoxalyl chloride were added to 10 ml of 1,2-dichloroethane and then themixture was stirred for 8 hours at 100° C. The reaction solution wascooled down to room temperature. The reaction solvent and excessiveoxalyl chloride were removed by distillation under reduced pressure toobtain 2-chlorobenzoyl isocyanate in an oily state. 10 ml of fresh1,2-dichloroethane and 0.28 g (1.5 mmol) of 2,5-dichloro-4-cyano anilinewere successively added thereto, reacted for 2 hours and filtered toobtain 0.43 g (Yield 78%) of the title compound as a solid.

M.P.: 244-247° C.

¹ H-NMR (DMSO-d₆, 300 MHz, ppm): δ 11.83(s,1H), 11.45 (s,1H),8.64(s,1H), 8.37(s,1H), 7.68-7.43(m,4H)

The aryl benzoyl urea derivatives of the present invention preparedaccording to the examples as described above show an excellentpesticidal activity against pests such as diamond-back moth (Plutellaxylostella), Tobacco cutworm (Spodoptera litura), and the like. Theirpesticidal activity can be determined by the following experiments.

The test preparations, that is pesticidal compositions, used in theexperiments hereinafter can be prepared in a variety of formulationforms according to their purposes. For convenience, the compound of thepresent invention was mixed with suitable amount of surfactant, waterand acetone to produce a test preparation containing the test compoundin a predetermined concentration in the following experiments. Thecompound was first tested at the concentration of 500 ppm, and then incase 100% of lethality was shown at that concentration, concentrationwas decreased gradually until all the pests tested were survived.

In addition, the test result at low concentrations of the compoundaccording to the present invention was compared with that of Dimilin™which is universally used, in order to confirm the strong pesticidalactivity of the present invented compound.

EXPERIMENT 1 Test for Pesticidal Activity Against Diamond-Back Moth(Plutella xylostella)

Fresh cabbage leaves were cut off in the form of a round disk having adiameter of 5 cm. 25 mg of the test compound was dissolved in 50 ml of amixture containing acetone and triton-X 100 in the ratio of 1:9 toproduce a test preparation containing the test compound in theconcentration of 500 ppm. Cabbage leaf disks as prepared above weretreated by being dipped into the test preparation for 30 seconds andthen dried in a hood. The dried cabbage leaf disks were put into adisposable petri dish having a diameter of 5 cm and then 20 three-agedlarvae of diamond-back moth (Plutella xylostella) were inoculatedthereto using a fine brush. Then, the dish was tightly closed with a lidto prevent the escape of larvae.

The petri dish with its contents was maintained at 25° C. under 60%humidity. After 120 hours, abnormal growth and lethality of Plutellaxylostella were examined.

The efficacy of the test compound was estimated according to thefollowing criterion and their controlling effect at a concentration of500 ppm are described in the following Table 2.

5: 95% to 100% control value

4: 80% to less than 95% control value

3: 50% to less than 80% control value

2: 30% to less than 50% control value

1: 10% to less than 30% control value

0: less than 10% control value

                  TABLE 2                                                         ______________________________________                                        Pesticidal activity against Diamond-back Moth                                   (Plutella xylostella)                                                                          Control value                                                Test compound 500 ppm                                                       ______________________________________                                        Compound of                                                                     Example 1 4                                                                   Example 2 1                                                                   Example 3 1                                                                   Example 4 2                                                                   Example 5 1                                                                   Example 6 5                                                                   Example 7 3                                                                   Example 8 1                                                                   Example 9 1                                                                   Example 10 1                                                                  Example 11 4                                                                  Example 12 1                                                                  Example 13 1                                                                  Example 14 5                                                                  Example 15 5                                                                  Example 16 5                                                                  Example 17 5                                                                  Example 18 5                                                                  Example 19 5                                                                  Example 20 4                                                                  Example 21 3                                                                  Example 22 5                                                                  Example 23 4                                                                ______________________________________                                    

Concentration-dependent lethality (%) against diamond-back moth of somecompounds among those described in Table 2 was determined and comparedwith that of control compound, Dimilin™, and the results are describedin the following Table 3.

                  TABLE 3                                                         ______________________________________                                        Test  Concentration (ppm) -dependent lethality (%)                            Com.  500    250    63   16   4    1    .25  .063 .016                        ______________________________________                                        Dimilin                                                                             100     80     0                                                          EX.1 100 100  80  60  0                                                       EX.14 100 100 100 100  95 40                                                  EX.15 100 100 100 100 100 100  100  50                                        EX.16 100 100 100  30                                                         EX.17 100 100 100 100 100 55 10                                               EX.18 100 100 100 100 100 95 75 50 20                                       ______________________________________                                    

EXPERIMENT 2 Test for Pesticidal Activity Against Tobacco Cutworm(Spodoptera litura)

Fresh cabbage leaves were cut off in the form of round disk having adiameter of 5 cm. 25 mg of the test compound was dissolved in a mixturecontaining acetone and triton-X 100 in a ratio of 1:9 to produce a testpreparation having the test compound in a concentration of 500 ppm. Thecabbage leaf disks as prepared above were treated by being dipped intothe test preparation for 30 seconds and then dried in a hood. The driedcabbage leaf disks were put into a disposable petri dish having adiameter of 5 cm and then 20 three-aged larvae of Tobacco cutworm(Spodoptera litura) were inoculated thereto by using a fine brush. Then,the dish was tightly closed with a lid to prevent the escape of larvae.

The petri dish with its contents was maintained at 25° C. under 60%humidity. After 120 hours, abnormal growth and lethality of Tobaccocutworm were examined.

The efficacy of the test compound was estimated according to thecriterion as represented in Experiment 1 above and their controllingeffect at a concentration of 500 ppm are described in the followingTable 4.

                  TABLE 4                                                         ______________________________________                                        Pesticidal activity against Tobacco cutworm                                     (Spodoptera litura)                                                                            Control value                                                Test compound 500 ppm                                                       ______________________________________                                        Compound of                                                                     Example 1 5                                                                   Example 2 5                                                                   Example 3 5                                                                   Example 4 3                                                                   Example 5 1                                                                   Example 6 2                                                                   Example 7 3                                                                   Example 8 4                                                                   Example 9 1                                                                   Example 10 4                                                                  Example 11 4                                                                  Example 12 2                                                                  Example 13 1                                                                  Example 14 5                                                                  Example 15 5                                                                  Example 16 5                                                                  Example 17 5                                                                  Example 18 5                                                                  Example 19 5                                                                  Example 20 3                                                                  Example 21 3                                                                  Example 22 5                                                                  Example 23 4                                                                ______________________________________                                    

Concentration-dependent lethality (%) against Tobacco cutworm of somecompounds among those described in Table 4 was determined and comparedwith that of control compound. The results are described in thefollowing Table 5.

                                      TABLE 5                                     __________________________________________________________________________    Test                                                                              Concentration(ppm)-dependent lethality (%)                                Com.                                                                              500                                                                              250 63 16  4  1   .25                                                                              .063 .016                                                                             .008                                      __________________________________________________________________________    Dimilin                                                                           100                                                                              100 100                                                                              90  50 0                                                          EX. 1        100  100   100   100   100  100  100    50    30                 EX. 2       100  100   100   100   100   40                                   EX. 3       100  100   100   100   100  100   40                              EX. 14     100  100   100   100   100   85   45                               EX. 15     100  100   100   100   100  100  100    95    55     5                                                EX. 16     100  100   100   100                                              100  100   55    30                         EX. 17     100  100   100   100   100  100  100    75    15    15           __________________________________________________________________________

As can be seen from the above results, aryl benzoyl urea derivativeaccording to the present invention exhibits- a superior pesticidaleffect especially against diamond-back moth and tobacco cutworm morethan 100 to 500 times to Dimilin which is the existing inhibitor forchitin formation. Furthermore, the process for preparing the compound ofthe present invention is simpler than that for preparing the existingbenzoyl ureido diphenyl ether derivative, therefore the present inventedcompound has the advantage of being obtained much more economically.

We claim:
 1. An aryl benzoyl urea derivative represented by thefollowing formula (I): ##STR10## in which X¹ and X² independently of oneanother represent hydrogen, fluoro or chloro,R¹ represents chloro, R²represents trifluoromethyl, and R³ represents fluoro.
 2. The arylbenzoyl urea derivative of claim 1, wherein the compound of formula (I)is1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2,6-difluorobenzoyl)urea.3. The aryl benzoyl urea derivative of claim 1, wherein the compound offormula (I) is1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2-fluorobenzoyl)urea.4. The aryl benzoyl urea derivative of claim 1, wherein the compound offormula (I) is1-(2-chloro-4-fluoro-3-trifluoromethylphenyl)-3-(2-chlorobenzoyl)urea.5. A pesticidal composition comprising as an active ingredient an arylbenzoyl urea derivative represented by the following formula (I):##STR11## in which X¹, X², R¹, R², and R³ are defined as described inclaim 1, in combination with an agriculturally acceptable carrier.